Analysis of acidic metal carbonyl hydride containing streams

ABSTRACT

A method for determining the concentration of an acidic metal carbonyl hydride in an organic liquid by measuring the conductivity or pH of the liquid. The air addition to a continuous air demetallating unit may be controlled by feedback from the conductivity or pH measurement of the effluent.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a method for measuring the amount ofacidic metal carbonyl hydrides and derivatives thereof in a liquid. Inone aspect, it pertains to the relationship between the transition metalcarbonyl hydride concentration in an organic stream and the conductivityand/or the pH of the stream. In another aspect, it pertains to a methodof controlling the air demetallating of a crude product stream bymeasurement of either the conductivity or pH of the demetallated stream.

2. Description of the Background

Catalytic processes involving acidic transition metal carbonyl hydridesand derivatives thereof are well known. For example, acidic metalcarbonyl hydrides are active catalysts for the homologation of alcohols,the carbonylation of cyclic ethers, dialkyl acetals, ortho esters, andesters, and the hydrogenation, hydrosilation, hydrocarboxylation, andhydroformylation of alkenes. Typical metal carbonyl hydrides employedfor such reactions include those of the metals of Groups VI, VII, andVIII. For example, the hydroformylation or oxo process is used for thepreparation of oxygenated organic compounds by the reaction of carbonmonoxide and hydrogen (synthesis gas) with carbon compounds containingolefinic linkages in the presence of a carbonylation catalyst. Reactionconditions typically comprise synthesis gas pressures of from about 1500to 4500 psig and temperatures of from about 150° to 450° F.

The oxo process is a particularly attractive method for the preparationof valuable aldehydes. A great variety of olefins may be used in theprocess. Thus, straight- and branched-chain olefins and diolefins,olefinic fractions from the hydrocarbon synthesis process, thermal orcatalytic cracking operations, and other sources of hydrocarbonfractions containing olefins may be used as starting materials. Not onlyolefins, but most organic compounds possessing at least one non-aromaticcarbon-carbon double bond may also be reacted by this method. Typically,the catalyst may be added in the form of a cobalt compound such ascobalt carbonyl, a cobalt soap, or a phosphine coordination complex of acobalt compound. Under the conditions of the reaction, the catalyst ispresent as an acidic cobalt carbonyl hydride, e.g., HCo(CO)₄ or HCo(CO)₃PR₃. Catalysts which do not contain alkyl or aryl phosphine ligands aregenerally referred to as unmodified catalysts. The oxo process isdiscussed in great detail in U.S. Pat. Nos. 3,518,319 and 3,239,569,which are incorporated by reference herein.

Efficient recycling of the catalysts often requires that the catalyst beremoved from the crude product before purification of the product. Forexample, distillation of a crude product before removal of an acidicmetal carbonyl hydride may result in loss of catalyst due to thermaldecomposition.

In particular, the unmodified cobalt carbonyl catalyst has been widelyused for synthesis of aldehydes by the oxo process using what isgenerally referred to as an overflow reactor design. The crude aldehyde,reaction solvent, and cobalt carbonyl hydride as effluent from the oxoreactor are sent to the crude aldehyde refining distillation columns. Itis well known in the art that the cobalt carbonyl hydride contained inthe crude aldehyde product stream must be removed prior to aldehyderectification. Thermal treatment of the cobalt carbonyl hydride in thebase of the aldehyde rectification column results in the decompositionof the cobalt carbonyl hydride to metal plate, and to some degree asmall quantity of cobalt carbonyl hydride will volatilize into theoverhead product. In either case the addition of cobalt carbonyl hydrideto the base of an aldehyde rectification column is undesirable.

A number of methods have been devised for the recovery and recycling ofcobalt catalysts from organic streams. U.S. Pat. No. 3,369,050 disclosesthe process of distilling the product from the catalyst in the presenceof a controlled concentration of a protecting agent such as a mixture ofpropylene and carbon monoxide, and thereby protecting the catalyst fromdecomposition. U.S. Pat. No. 3,539,634 describes the removal of tarryconstituents from the liquid residue after distillation by passing theresidue over a solid adsorbent which is effective in selectiveadsorption of the tarry constituents without significant adsorption ofthe catalyst. The use of a cobalt catalyst which is supported on aluminaand is thus easily separable from the product stream is disclosed inU.S. Pat. No. 3,991,119. U.S. Pat. No. 4,060,557 describes the use of awiped film evaporator for separating the products from the catalysts.The evaporator has rotating wiper blades which mechanically produce athin film and continuously wipe this film on a heated surface. Thismechanical wiping action provides a more rapid removal of the catalystresidue or bottoms. The process thus allows for minimal build-up ofcatalyst residue, reduced catalyst decomposition, and rapid continuousprocessing.

A preferred process for catalyst recovery from the product streaminvolves treating the product stream with oxygen to convert the cobaltcarbonyl hydride to a water soluble cobalt salt. The cobalt salt maythen be removed from the product stream by contact with water. Thisprocess is known as air decobalting. U.S. Pat. No. 4,225,458 teaches amethod for the regeneration of the catalyst from the cobalt salt whichcomprises contacting the water solution of the cobalt salt with a soapderived from the heavy oxygenated bottoms fraction from the distillationunit.

Of the above-mentioned methods for the recovery of recycle of the cobaltcatalyst, the air decobalting method is preferred. However, the quantityof air used for the decobalting must be controlled. As disclosed in U.S.Pat. No. 3,409,648, addition of excess air to the product stream resultsin oxidation of desired aldehyde product to undesired carboxylic acid.Thus, the quantity of air added to the product stream must be limited tothe minimum amount necessary to convert all of the cobalt carbonylhydride to cobalt salts. Addition of too little air will result inincomplete conversion of cobalt carbonyl hydride to cobalt salts andloss of valuable catalyst through decomposition in the distillationstep. Addition of too much air will result in oxidation of the desiredaldehyde product to undesired carboxylic acid.

Minimizing the quantity of air added in the decobalting step requires amethod for measuring the degree of conversion of the cobalt carbonylhydride to cobalt salts in the product stream. For use in a continuousair decobalting unit, a fast method of measuring the conversion ofcobalt carbonyl hydride to cobalt salts which can be used in a feedbacksystem is especially desirable. With such a method of measurement thequantity of air added in the decobalting step could be minimized evenwhen the concentration of cobalt carbonyl hydride in the product streamor the liquid flow rate of the product stream are unknown or change withtime.

To date, the analytical methods used to determine the degree ofconversion of cobalt carbonyl hydride to cobalt salts have includedwet-chemistry techniques and/or well known instrumental techniquesincluding atomic adsorption and emission spectroscopy, ultravioletspectroscopy, and infrared spectroscopy. Each of these methods suffersfrom drawbacks which make their utilization undesirable. For example,the wet chemistry analytical methods are cumbersome, time-consuming, andill suited for use as a means of feedback in a continuous airdecobalting unit. Measurements based on atomic absorption and emissionspectroscopy determine only the total cobalt concentration, and, thus,do not provide any information on the degree of conversion of cobaltcarbonyl hydride to cobalt salts. Measurements using ultraviolet orinfrared spectroscopy require either cumbersome sample preparation whichwould be ill suited for a continuous system or expensive high-pressurewindows, since the stream is under pressure.

Thus, there is a need for a method of determining the amount of acidicmetal carbonyl hydride in the product stream of a catalytic processwhich can be used as a means of feedback in a continuous catalystremoving unit. In particular, there is a need for a method of measuringthe degree of conversion of cobalt carbonyl hydride to cobalt salts inthe product stream of the oxo process which can be used as a means offeedback in a continuous air decobalting unit.

SUMMARY OF THE INVENTION

In accordance with the present invention, it has been discovered thatthere is a relationship between the acidic metal carbonyl hydrideconcentration in an organic liquid and the conductivity and pH of thesolution. The relationship found between the metal carbonyl hydrideconcentration and the conductivity and pH of the solution allows for asimple and accurate measurement of metal carbonyl hydride concentrationwithout the use of cumbersome wet-chemistry analytical techniques orexpensive spectroscopic equipment. Thus, the method of the presentinvention may be used to control the removal of acidic metal carbonylhydrides from organic liquids in a demetallating process.

In particular, the present invention provides a method for thedetermination of the concentration of cobalt carbonyl hydride in anorganic liquid by measuring either the conductivity or pH of the organicliquid. The present invention allows for the degree of cobalt carbonylhydride conversion to cobalt salts to be determined in a process streamin a continuous fashion. It has also been found that the conductivityand the pH of the crude aldehyde solution significantly decrease andincrease, respectively, during the air decobalting step. Thus, thedegree of decobalting can be determined in a process stream in acontinuous fashion by using an on-line conductivity meter or an on-linepH meter. Efficient control of the continuous air decobalting processcan be achieved by means of a feedback system from the on-line meter.

Upon further study of the specification and claims, further objects andadvantages of this invention will become apparent to those skilled inthe art.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The method of the present invention is generally applicable to anyacidic transition metal carbonyl hydride and derivatives thereof.Suitable metal carbonyl hydrides are those of Groups VI, VII, and VIIIof the transition metals. Specifically, acidic metal carbonyl hydridesof Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, and Pt aresuitable for use in the practice of the present invention. The metalcarbonyl hydride may catalyze a process such as the homologation ofalcohols, the carbonylation of cyclic ethers, dialkyl acetals, orthoesters, and esters, and the hydrogenation, hydrosilation, andhydroformylation of alkenes. It is preferred that the catalytic processbe hydroformylation, i.e., the oxo process.

In its preferred embodiment, the present invention is applicable to theoxo conversion of any aliphatic or cycloaliphatic compound having atleast one ethylenic carbon-carbon bond. Thus, it may be applied to theoxo process conversion of olefins having, e.g., from 2 to 20 carbons toreaction mixtures predominating in aliphatic aldehydes having one morecarbon than the starting olefin. Suitable monoolefins include ethylene,propylene, and butylene. Suitable hydrocarbons include both branched-and straight-chain compounds having one or more terminal or internalolefinic sites. These sites may be conjugated, as in 1,3-butadiene, ornon-conjugated, as in 1,5-hexadiene. In the case of polyolefins, it ispossible to hydroformylate only one of the olefinic sites or several orall of the sites. The present invention may also be applied to the oxoconversion of ethylenic carbon-carbon bonds of functionalizedhydrocarbons, such as unsaturated alcohols, unsaturated aldehydes, andunsaturated acids. It is preferred to apply the present invention to theoxo conversion of ethylene and propylene, because of the widespread useof such processes, frequently as continuous operations.

The process of the present invention may be applied to any oxo processusing any catalyst source that is converted to an acidic metal carbonylhydride under the reaction conditions. Catalyst sources that areconverted to acidic carbonyl hydrides of Co, Fe, Ru, Rh, Ir, and Pt arepreferred. Catalyst sources that are converted to acidic cobalt carbonylhydrides are presently most preferred.

The metal, e.g., cobalt may be added to the reaction mixture in avariety of forms, e.g., as a cobalt salt, cobalt oxide, or dicobaltoctacarbonyl. Other suitable catalyst sources include amine, arsine,stibine, phosphine, and phosphite derivatives of the metal carbonyl.

The amines, arsines, and stibines may be any trialkyl-, triaryl-,dialkylaryl-, or alkyldiaryl-substituted moiety. Similarly, anytrialkyl, triaryl, dialkylaryl, or alkyldiaryl phosphine or phosphitederivative of the metal carbonyl, particularly cobalt carbonyl, may beused as a catalyst source. U.S. Pat. No. 3,239,569 discloses a number ofsuitable catalyst sources which are phosphine derivatives and isincorporated herein by reference. The phosphine and phosphitederivatives of cobalt carbonyl are preferred, and cobalt carbonyl isparticularly preferred.

The present invention comprises measuring either the conductivity or thepH of the organic fluid to be analyzed. It has been found that theconductivity of the organic liquid increases with increasingconcentration of acidic metal carbonyl hydride. Thus, the concentrationof acidic metal carbonyl hydride in the organic liquid can beascertained by measuring the conductivity of the liquid.

Alternatively, the cobalt carbonyl hydride concentration may bedetermined by measuring the pH of the organic liquid by means of a pHmeter. An increase in the pH of the organic liquid indicates a decreasein the concentration of acidic metal carbonyl hydride.

The present invention may be applied to any acidic metal carbonylhydride containing organic liquid. It is preferred to apply the methodof the present invention to product streams of catalytic processes,particularly aldehyde containing liquids.

A particular advantage of the present invention is the unexpected resultthat the contribution of metal salts to the conductivity of the organicliquid is insignificant. Thus, thoroughly mixing a sample of airdemetallated effluent with a water solution of ten times the normaleffluent metal salt concentration produces an insignificant rise in theconductivity of the organic liquid. A further unexpected result of thepresent invention is that the pH of the liquid increases (becomes morebasic) during air demetallating. It would be expected that the organicacids produced during air demetallating would increase the solutionacidity and lower the pH.

The process of the present invention may be applied to the demetallatingof an organic liquid in a batch process. Thus, during the airdemetallating of a specific quantity of an organic liquid which alsocontains a quantity of metal carbonyl hydride, samples may be withdrawnand the concentration of metal carbonyl hydride determined by measuringeither the conductivity or the pH of the liquid. The air demetallatingof the organic liquid may be stopped when the measured conductivity ofthe sample is sufficiently low (or the measured pH of the sample issufficiently high) to indicate an acceptably low concentration of metalcarbonyl hydride. Alternatively, the conductivity or the pH of theorganic liquid may be measured continuously during the air demetallatingprocess and the process may be stopped when the measured conductivity issufficiently low or the measured pH is sufficiently high.

In a preferred embodiment, the present method may be used in conjunctionwith a continuous air demetallating process. In a continuous airdemetallating process, the crude product stream is mixed with air andfed into a demetallating unit. Oxidation of the acidic metal carbonylhydride gives metal salts which are removed by washing with water. Theconversion of metal carbonyl hydride to metal salts may be monitored bymeasuring either the conductivity or pH of the effluent from thedemetallating unit. The measured conductivity or pH may be used tocontrol the quantity of air fed into the continuous air demetallatingunit by means of a feedback system.

Thus, if the measured conductivity rises to a level indicative of anunacceptably high concentration of metal carbonyl hydride in theeffluent stream, the rate of air addition to the air demetallating unitcan be increased until the measured conductivity drops to a levelindicative of an acceptably low concentration of metal carbonyl hydridein the effluent. Alternatively, if the measured pH drops to a valueindicative of an unacceptably high concentration of metal carbonylhydride in the effluent, the rate of air addition to the airdemetallating unit can be increased until the measured pH returns to avalue indicative of an acceptably low concentration of metal carbonylhydride in the effluent.

Similarly, when either the measured conductivity decreases or themeasured pH increases to a value indicative of nearly completedemetallating and possible oxidation of product, the rate of airaddition to the air demetallating unit can be decreased until either themeasured conductivity increases or the measured pH decreases to a valueindicative of minimal product oxidation.

One advantage of the present invention in conjunction with a continuousair demetallating unit is that neither the liquid flow rate nor themetal carbonyl hydride concentration entering the air demetallating unitneed be accurately known to achieve an optimum oxygen to metal molarratio. A further advantage of the present invention in conjunction witha continuous air demetallating unit is that an optimum oxygen to metalmolar ratio may be achieved even when the liquid flow rate or the metalcarbonyl hydride concentration entering the air demetallating unitvaries with time.

Other features of the invention will become apparent in the course ofthe following descriptions of exemplary embodiments which are given forillustration of the invention and are not intended to be limitingthereof.

EXAMPLES Example 1--Cobalt Carbonyl Hydride Concentration Versus pH andConductivity

This example illustrates the relationship between the cobalt carbonylhydride concentration and the conductivity and pH in an organicsolution. A sample of crude aldehyde feed to a continuous air decobalterwas batch air decobalted in the laboratory. The rate of decobalting wasfollowed by conductivity (bench top YSI conductivity meter) and pHmeasurements. The concentration of metal carbonyl hydride, in units ofCo₂ (CO)₈, was determined by decomposing the cobalt carbonyl hydride andmeasuring the quantity of carbon monoxide off gas. The total cobaltconcentration was determined by atomic absorption spectroscopy. Theresults of this experiment are shown in Table I.

                  TABLE I                                                         ______________________________________                                        Relationship Between Cobalt Carbonyl Hydride                                  Concentration and Conductivity and pH                                         Cobalt Carbonyl Hydride                                                                          Conductivity                                               (ppm Co.sub.2 (CO).sub.8)                                                                        (microohms)                                                                              pH                                              ______________________________________                                         2                  4         5.80                                             6                  6         5.75                                             18                20         5.70                                             58                29         5.60                                            112                35         5.10                                            170                42         4.45                                            200                46         3.90                                            ______________________________________                                    

Example 2--Conductivity and pH Measurements of the Crude Aldehyde Feedand Effluent of a Continuous Air Decobalting Unit

The crude aldehyde feed and effluent of a continuous air decobalter wereanalyzed for conductivity and pH over a six-day period. The conductivitywas measured with a TBI conductivity meter. The cobalt carbonyl hydrideconcentration was determined as described in Example 1. The averageresults of the six-day monitoring period are shown in Table II, anddemonstrate that the conductivity and pH measurements obtained from thecontinuous air decobalter reproduce the values obtained in the batch airdecobalting experiment.

                  TABLE II                                                        ______________________________________                                        Analysis of the Air Decobalter Feed and Effluent                              Decobalter Feed Decobalter Effluent                                           Total  Conduc-          Cobalt, ppm                                                                              Conduc-                                    Cobalt,*                                                                             tivity                 Carbonyl                                                                             tivity                                   ppm    microohms pH     Total Hydride                                                                              microohms                                                                             pH                               ______________________________________                                        284    54        4.1    34    8.2    8.8     5.9                              ______________________________________                                        *As Cobalt Carbonyl                                                       

Example 3--Effect of Cobalt Salts on the Conductivity of the AirDecobalterEffluent

A sample of effluent (100 ml) from the air decobalter taken during thesix-day monitoring period having a conductivity of 7.6 microohms wascombined with 50 ml of water containing 6,000 ppm cobalt primarily inthe form of cobalt formate and thoroughly mixed. The resulting solutionhad a conductivity of 7.8 microohms, as measured by a bench top YSIconductivitymeter. The quantity of cobalt salt used in this examplerepresents 10 timesthe normal quantity present in the decobaltereffluent, thus it is readily recognized that the contribution of thecobalt salts to the organic solution conductivity is insignificant.

Obviously, numerous modification and variations of the present inventionare possible in light of the above teachings. It is therefore to beunderstood that within the scope of the appended claims, the inventionmaybe practiced otherwise than as specifically described herein.

We claim:
 1. A method for determining the change in concentration of anacidic transition metal carbonyl hydride in an organic liquid comprisingthe following steps:a) providing an organic liquid suspected ofcontaining an acidic transition metal carbonyl hydride; b) measuring aninitial electrical conductivity or pH level of the liquid; c) measuringat a time later than the initial measurement the electrical conductivityor pH of the liquid; and d) determining the change in electricalconductivity or pH wherein an increase in conductivity is an indicationof increasing acidic metal carbonyl hydride concentration or wherein anincrease in pH is an indication of decreasing acidic metal carbonylhydride concentration.
 2. The method of claim 1, wherein said measuringdevice is an on-line conductivity meter.
 3. The method of claim 1,wherein said measuring device is an on-line pH meter.
 4. The method ofclaim 1, wherein said liquid is a product stream from a catalyticprocess selected from the group consisting of homologation of alcohols,carbonylation of cyclic ethers, carbonylation of dialkyl acetals,carbonylation of ortho esters, carbonylation of esters, hydrogenation ofalkenes, hydrosilation of alkenes and hydroformylation of alkenes. 5.The method of claim 4, wherein said catalytic process ishydroformylation.
 6. The method of claim 5, further comprising airdemetallating said stream before measuring the electrical conductivityor pH.
 7. The method of claim 6, wherein said air demetallating step isan air decobalting step.
 8. The method of claim 7, wherein said airdecobalting is a continuous process.